3,3,3',3'-tetramethyl-1,1'-spirobiindane-based monophosphine ligand, intermediates thereof, preparation method and use of the same

Abstract

Provided are a 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-based monophosphine ligand and intermediates thereof, and preparation methods and uses of the same. The monophosphine ligand is a compound represented by formula I or formula I′, or an enantiomer, a raceme or a diastereoisomer thereof, including phosphonite ligands, phosphite ligands, phosphoramidite ester ligands, phosphoric acid and phosphonic amide. The monophosphine ligand is prepared with a known 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-7,7′-diol derivative as a raw material through a scheme in which the compound presented by formula II acts as an intermediate. The present disclosure provides a novel monophosphine ligand, which can be used as a ligand in a metal-catalysed organic reactions or in directly catalyzing an organic reaction, especially as a chiral monophosphine ligand widely used in many chiral catalytic reactions such as asymmetric addition, asymmetric hydrogenation, asymmetric coupling, and asymmetric allyl alkylation, having economic practicality and industrial application prospects.

What is claimed is: 
     
       1. A 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-based monophosphine ligand, being a compound represented by formula I or formula I′, or an enantiomer, a raceme or a diastereoisomer thereof: 
       
         
           
           
               
               
           
         
         wherein in formula I and formula I′: R 1  and R 6  are each independently selected from the group consisting of hydrogen, C 1 -C 10 alkyl or perfluoroalkyl, C 3 -C 6  cycloalkyl, and C 1 -C 4  alkoxy or perfluoroalkoxy, unsubstituted or substituted aryl; and R 2 , R 3 , R 4 , and R 5  are each independently selected from the group consisting of hydrogen, halogen, C 1 -C 10 alkyl or perfluoroalkyl, C 3 -C 6  cycloalkyl, and C 1 -C 4  alkoxy or perfluoroalkoxy, 
         wherein in formula I: X is selected from the group consisting of arylvinylphenyl, aryloxy, arylvinylphenoxy, and NR 7 R 8 ; R 7  and R 8  are each independently selected from the group consisting of C 1 -C 4  alkyl, arylmethylene, and arylmethylmethenyl; and 
         wherein in formula I′: Y is hydroxyl or NHR 9 , R 9  is hydrogen. 
       
     
     
       2. The 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-based monophosphine ligand according to  claim 1 , being a phosphonite ligand represented by formula I-A or an enantiomer thereof: 
       
         
           
           
               
               
           
         
         wherein in the formula I-A: R 1  is selected from the group consisting of hydrogen, C 1 -C 10 alkyl or perfluoroalkyl, C 3 -C 6  cycloalkyl, and C 1 -C 4  alkoxy or perfluoroalkoxy; R 2  is hydrogen or C 1 -C 4  alkyl; and R 10  is arylvinylphenyl. 
       
     
     
       3. The 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-based monophosphine ligand according to  claim 1 , being a phosphite ligand represented by formula I-B or an enantiomer thereof: 
       
         
           
           
               
               
           
         
         wherein in formula I-B: R 1  is selected from the group consisting of hydrogen, C 1 -C 10  alkyl or perfluoroalkyl, C 3 -C 6  cycloalkyl, and C 1 -C 4  alkoxy or perfluoroalkoxy; R 2  is hydrogen or C 1 -C 4  alkyl; and R 11  is represented by a structural formula I-BB: 
       
       
         
           
           
               
               
           
         
         wherein in formula IBB: X 1 -X 4  are each selected from the group consisting of hydrogen, C 1 -C 10 alkyl or perfluoroalkyl, C 3 -C 6  cycloalkyl, and C 1 -C 4  alkoxy or perfluoroalkoxy; R 12  is aryl or C 5 -C 14  heteroaryl. 
       
     
     
       4. The 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-based monophosphine ligand according to  claim 1 , being a phosphite ligand represented by formula I-C or an enantiomer thereof: 
       
         
           
           
               
               
           
         
         wherein in formula I-C: R 1  is selected from the group consisting of hydrogen, C 1 -C 10  alkyl or perfluoroalkyl, C 3 -C 6  cycloalkyl, and C 1 -C 4  alkoxy or perfluoroalkoxy, arylmethyleneoxy, unsubstituted or substituted aryl, and unsubstituted or substituted heteroaryl; 
         R 2  is hydrogen or C 1 -C 4  alkyl; and 
         R 13  and R 14  are each independently selected from the group consisting of C 1 -C 4  alkyl, arylmethylene, and arylmethylmethenyl. 
       
     
     
       5. A synthesis method of the compound presented by formula 1 according to  claim 1 , the synthesis method comprising:
 preparing a compound represented by formula I through a substitution reaction of a compound presented by formula II, as a raw material, with substituted phosphoric dichloride Cl 2 P—X under an alkali, according to the following reaction scheme: 
 
       
         
           
           
               
               
           
         
         wherein in the formulas: R 1 -R 6  are the same as those defined in  claim 1 ; X is selected from the group consisting of arylvinylphenyl, and NR 7 R 8 ; and R 7  and R 8  are the same as those defined in  claim 1 ; or 
         preparing a compound represented by formula II-I through a substitution reaction of the compound represented by formula II, as a raw material, with phosphorus trichloride under an alkali, and then preparing the compound represented by formula I through a reaction of the compound represented by formula II-I with HX and an alkali, according to the following reaction scheme: 
       
       
         
           
           
               
               
           
         
         wherein in the formulas: R 1 -R 6  are the same as those defined in  claim 1 ; X is selected from the group consisting of aryloxy, arylvinylphenoxy, and NR 7 R 8 ; and R 7  and R 8  are the same as those defined in  claim 1 . 
       
     
     
       6. A synthesis method of the compound represented by formula I′ according to  claim 1 , the synthesis method comprising:
 preparing a compound represented by formula II-I′ through a substitution reaction of the compound presented by formula II, as a raw material, with phosphorus oxychloride, and then preparing the compound represented by formula I′ through a hydrolysis of the compound represented by formula II-I′, according to the following reaction scheme: 
 
       
         
           
           
               
               
           
         
         wherein in the formulas: R 1 -R 6  are the same as those defined in  claim 1 ; or 
         preparing the compound represented by formula I′ through a substitution reaction and a reduction reaction of the compound represented by formula II-I′ with sodium azide, according to the following reaction scheme: 
       
       
         
           
           
               
               
           
         
         wherein in the formulas: R 1 -R 6  are the same as those defined in  claim 1 . 
       
     
     
       7. The 3,3,3′,3′-tetramethyl-1,1′-spirobiindane-based monophosphine ligand according to  claim 1 , wherein the compound represented by formula I is selected from the group consisting of the following compounds and an enantiomer thereof: 
       
         
           
           
               
               
           
         
       
       and
 wherein the compound represented by formula I′ is selected from the group consisting of the following compounds and an enantiomer thereof: